CN1147952C - Carbonaceous electrode material for non-aqueous secondary battery - Google Patents

Carbonaceous electrode material for non-aqueous secondary battery

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Publication number
CN1147952C
CN1147952C CNB988048183A CN98804818A CN1147952C CN 1147952 C CN1147952 C CN 1147952C CN B988048183 A CNB988048183 A CN B988048183A CN 98804818 A CN98804818 A CN 98804818A CN 1147952 C CN1147952 C CN 1147952C
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carbonaceous
measured
carbonaceous material
electrode
comes
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CN1255244A (en
Inventor
山田心一郎
二
井本浩
幸
东秀人
雄
妹尾直
弘
世界孝二
朗
永峰政幸
小丸笃雄
园部直弘
增子二朗
石川实
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Kureha Corp
Sony Corp
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Kureha Corp
Sony Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Inert Electrodes (AREA)
  • Secondary Cells (AREA)

Abstract

A carbonaceous electrode having improved capacities for doping and dedoping of a cell active substance, such as lithium, and suitable for a non-aqueous solvent secondary battery, is constituted by a carbonaceous material having a true density as measured by a butanol substitution method of at most 1.46 g/cm<3>, a true density as measured by a helium substitution method of at least 1.7 g/cm<3>, a hydrogen-to-carbon atomic ratio H/C of at most 0.15 as measured according to elementary analysis, a BET specific surface area of at most 50 m<2>/g as measured by nitrogen adsorption BET method. The carbonaceous material is advantageously produced by carbonizing an organic material originated from bamboo genera of family Gramineae, particularly genus Pleioblastus or Bambusa, at 1000-1400 DEG C. under a reduced pressure or under a flowing inert gas stream to provide an appropriate porous structure.

Description

Be used for carbonaceous electrode material, its manufacture method and the application thereof of non-aqueous secondary battery
Technical field
The present invention relates to a kind of carbonaceous material and manufacture method thereof that is suitable as the non-aqueous secondary battery electrode material.The invention still further relates to a kind of electrode structure and a kind of non-aqueous secondary battery that comprises this kind carbonaceous electrode material with this kind electrode structure.
Background technology
Along with electronic device and device size reduce, required to develop the more battery of high-energy-density, according to this kind requirement, various non-aqueous eletrolyte batteries have been proposed, comprise so-called lithium battery.
Yet the lithium metal that battery is used for negative electrode has some difficulties, and such as (1) relatively poor charge characteristic, for example common charging interval is 5-10 hour, reaches (2) short cycle life etc., especially when this battery constitutes secondary cell.These difficulties are all owing to lithium metal itself, and be considered to by the variation of the lithium form of for example following charge and discharge cycles to repeat, dendrite lithium form or the irreversible change of lithium causes.
As a kind of measure of eliminating above-mentioned difficulties, proposed to be used for the carbonaceous material (for example the Japan Patent spy opens clear (JP-A) 62-90863 and JP-A 62-122066) of negative electrode.Accompany the phenomenon that the carbon compound of lithium is easy to electrochemically form by utilization, developed this kind negative electrode.For example, when the negative electrode that comprises carbon charges in non-aqueous eletrolyte, between the layer that sandwiches negative electrode carbon and the layer (be negative electrode carbon with the doping of lithium electrochemical ground) with containing lithium electrochemical in the lithium anode.The carbon that is doped with lithium of Xing Chenging plays the effect of lithium electrode thus, and in battery discharge procedure, lithium goes out from discharging (or contra-doping) between the carbon-coating, turns back to anode.
Constitute electric current or capacitance (Ah/kg) that this kind contains the carbonaceous material per unit weight of carbon cathode, by the wherein capacity decision of elements doped lithium, big as far as possible lithium doping capacity (lithium atom being arranged but theoretical upper limit is per 6 carbon atoms) can be arranged on demand thereby contain carbon cathode material.
And, for guaranteeing that compact electronics device or device have enough operating times, and guarantee that its power pack has enough life-spans, wish that above-mentioned secondary cell has higher energy density and requires a kind of carbonaceous electrode material with higher lithium doping and contra-doping capacity of exploitation.
Summary of the invention
Consider the problems referred to above, in the process of researching and developing the high-performance carbonaceous electrode material that more is applicable to non-aqueous secondary battery, we have tested an organic material that comes from plant as new carbon source, and it has the feature of string.Found that, carbonaceous material by suitable calcining and certain fibrous vegetable material acquisition of carbonization, made and had the big unexpectedly doping and the carbonaceous material of contra-doping capacity, this carbonaceous material micropore is abundant, be suitable for battery (or element cell) active matter for example lithium mix, this and conventional carbonaceous electrode material are different, have realized the present invention thus.
Correspondingly, main purpose of the present invention provides the carbonaceous material with big doping and contra-doping capacity.
Another purpose of the present invention provides a kind of method and a kind of non-aqueous secondary battery with the electrode of planting the carbonaceous material formation thus of making this carbonaceous material.
According to the present invention, a kind of carbonaceous electrode material that is used for non-aqueous secondary battery is provided, wherein comprise a kind of carbonaceous material, this carbonaceous material has: be measured as≤1.46g/cm with the butanols displacement method 3Real density; Be measured as 〉=1.7g/cm with helium-displacement method 3Real density; Be measured as≤hydrogen-carbon atomic ratio H/C of 0.15 with elementary analysis; Be measured as≤50m with nitrogen absorption BET method 2The BET specific area of/g; And 〉=the carbon dioxide adsorption capacity of 10ml/g, and this carbonaceous material obtains by the organic material that carbonization comes from the grass family Sinobambusa, this organic material that comes from the grass family Sinobambusa comprises and at least aly comes from that bitter bamboo belongs to and the organic material of Bambusa genus.
Carbonaceous material according to the present invention is so-called ungraphitised carbon, and can be between carbon-coating and its micropore stored battery active matter.And carbonaceous material of the present invention is characterised in that: the real density of measuring with the butanols displacement method is 1.46g/cm to the maximum 3And the real density minimum of measuring with helium-displacement method is 1.70g/cm 3, this expression exists the butanols of suitable vast scale not infiltrate and micropore that helium can be invaded.This kind butanols can not infiltrate and micropore that helium can be invaded is useful to storage (promptly mixing) active matter, and correspondingly obtains bigger doping of active matter and contra-doping capacity owing to its effect.
The potassium content that preferably has the maximum 0.5wt% that measures with x-ray fluorescence analysis according to carbonaceous material of the present invention.
According to the present invention, a kind of method of making above-mentioned carbonaceous electrode material further is provided, comprising: the described organic material that comes from the grass family Sinobambusa of carbonization under low pressure or in inactive gas atmosphere, under 1000-1400 ℃ of temperature, described inactive gas is nitrogen, argon gas, helium or their mixture.
According to the present invention, also provide a kind of electrode structure that is used for anhydrous solvent type secondary cell, comprising: conductivity substrate with place at least one lip-deep combination electrode layer of conductivity substrate; And this combination electrode layer comprises the carbonaceous electrode material and the adhesive of particle form, and this carbonaceous electrode material comprises a kind of carbonaceous material, and this carbonaceous material has: be measured as≤1.46g/cm with the butanols displacement method 3Real density; Be measured as 〉=1.7g/cm with helium-displacement method 3Real density; Be measured as≤hydrogen-carbon atomic ratio H/C of 0.15 with elementary analysis; Be measured as≤50m with nitrogen absorption BET method 2The BET specific area of/g; And 〉=the carbon dioxide adsorption capacity of 10ml/g, and this carbonaceous material obtains by the organic material that carbonization comes from the grass family Sinobambusa, this organic material that comes from the grass family Sinobambusa comprises and at least aly comes from that bitter bamboo belongs to and the organic material of Bambusa genus.
According to the present invention, a kind of anhydrous solvent type secondary cell further is provided, comprising: anode, negative electrode, shim and place anode and negative electrode between non-aqueous eletrolyte; And at least one in described anode and the negative electrode comprises following electroplax structure, and this electrode structure comprises: conductivity substrate and place at least one lip-deep combination electrode layer of conductivity substrate; This combination electrode layer comprises the carbonaceous electrode material and the adhesive of particle form, and this carbonaceous electrode material comprises a kind of carbonaceous material, and this carbonaceous material has: be measured as≤1.46g/cm with the butanols displacement method 3Real density; Be measured as 〉=1.7g/cm with helium-displacement method 3Real density; Be measured as≤hydrogen-carbon atomic ratio H/C of 0.15 with elementary analysis; Be measured as≤50m with nitrogen absorption BET method 2The BET specific area of/g; And 〉=the carbon dioxide adsorption capacity of 10ml/g, and this carbonaceous material obtains by the organic material that carbonization comes from the grass family Sinobambusa, this organic material that comes from the grass family Sinobambusa comprises and at least aly comes from that bitter bamboo belongs to and the organic material of Bambusa genus.
Description of drawings
Fig. 1 illustrates the sectional perspective perspective view of the anhydrous solvent secondary cell that constitutes according to the present invention.
Fig. 2 is illustrated in the partial cross-sectional view of the electrode structure that adopts in the secondary cell.
Embodiment
Carbonaceous material according to the present invention is characterised in that: in order to real density (the following sometimes be called " ρ of butanols as the butanols displacement method measurement of replacement media B") be 1.46g/cm to the maximum 3With real density (the following sometimes be called " ρ of helium as the helium-displacement method measurement of replacement media H") minimum is 1.7g/cm 3Hydrogen-carbon atomic ratio H/C maximum 0.15 with the elementary analysis measurement; BET specific area (following " the S that is called sometimes BET") be 50m to the maximum 2/ g.
ρ BSurpass 1.46g/cm 3Carbonaceous material cause that littler doping-contra-doping capacity is arranged.ρ BPreferably≤1.45g/cm 3
ρ HBe lower than 1.7g/cm 3Carbonaceous material similarly cause doping-contra-doping capacity to reduce.P HPreferably 〉=be 1.8g/cm 3, more preferably 〉=1.9g/cm 3
Hydrogen-carbon atomic ratio H/C surpasses 0.15 carbonaceous material, for example handles organic substance under maximum 800 ℃ of temperature and the K cryogenic treatment carbon that obtains, perhaps specific area S BETSurpass 50m 2The carbonaceous material of/g, for example activated carbon is not preferred, because non--contra-doping capacity (promptly being retained in the amount of the active matter in the carbonaceous material that does not have contra-doping) increases.H/C is preferred≤and 0.13, more preferably≤0.1.Specific area S BETPreferably≤20m 2/ g, more preferably≤10m 2/ g.
Carbonaceous material another feature according to the present invention is: the carbon dioxide adsorption capacity 〉=10ml/g that measures under 0 ℃ and equalizing pressure 95kPa (this value is the gas specific volume that calculates under the standard state (STP) of 0 ℃ and 1atm (100kPa)).Have the carbonaceous material that is lower than 10ml/g carbon dioxide adsorption capacity to active matter for example lithium less doping capacity is only arranged.The carbonaceous material that this kind has less carbon dioxide adsorption capacity does not have enough flourishing micropore, or is formed with the blind hole that carbon dioxide can't be invaded.
Can believe that active matter for example lithium can be stored in or also can be adsorbed in the micropore of carbonaceous material of the present invention.Can believe that the carbonaceous material with above-mentioned less carbon dioxide adsorption capacity has the hole of less energy adsorption activity thing, thereby less active matter doping capacity is only arranged.Carbonaceous material preferably carbon dioxide adsorption capacity 〉=15ml/g of the present invention, more preferably 〉=20ml/g.
Carbonaceous material according to the present invention is measured potassium content with x-ray fluorescence analysis, is preferably≤0.5wt%.Bigger potassium content causes littler contra-doping capacity and bigger non--contra-doping capacity.Potassium content more preferably≤0.4wt%, further preferred≤0.3wt%, most preferably≤0.2wt%.
When measuring with the X-ray diffraction method, (002) interplanar distance 〉=0.365nm of carbonaceous material of the present invention is desirable, is preferably 0.370-0.395nm.
Carbonaceous material according to the present invention is made by the various organic materials of carbonization under the condition that forms at fit hole.
Any organic material all can be used as raw material, as long as they can produce volatile matter in its carbonisation.If can comprise organic material that nature exists for example petroleum asphalt and coal tar pitch and for example from natural organic industrial various organic materials the oil for example.
Oil or coal tar pitch can be by coal tar, decomposed the tar obtains or waited and make by for example distilling pitch that (comprising vacuum distillation, air-distillation and steam distillation), thermal polycondensation, extraction or chemical polycondensation process obtain by elevated temperature heat such as ethene Residual oil, crude oil.
Organic material can comprise any organic compound, if for example, comprising: for example conjugation resin, cellulose and the cellulose derivative of the furane resins of the homopolymers of furfuryl alcohol or furfural and copolymer, phenolic resins, acrylic resin, ethylene halide base resin, polyimide resin, polyamide-imide resin, polyamide, for example polyacetylene and p-poly-phenyl.
In addition, the example of other existing Organic Ingredients can comprise: for example concentrate polycyclic hydrocarbon compounds, naphthalene, phenanthrene, anthracene, triphenylene, pyrene, perylene (Asia puecon or bud), pentaphene, pentacene and derivative, for example their corresponding carboxylic acid, carboxylic acid anhydride and carboxyl imines; Various pitches that mainly comprise this kind compound and concentrate assorted polycyclic compounds, for example acenaphthene, indoles, iso-indoles, quinoline, isoquinolin, quinoxaline, furanidine, carbazole, acridine, azophenlyene and phenanthrene, and derivative.
Might be incorporated into oxygen-containing functional group in this kind asphalt material or the organic material as required.This can be for example by the wet method of the aqueous solution that uses nitric acid, sulfuric acid or inferior opinion acid or for example use the dry method of the oxidizing gas of air or oxygen to realize.Also might add for example iron chloride or the muriatic chlorine compound of zinc as required, perhaps add for example deoxidier of sulphur, ammonium nitrate or ammonium persulfate.
Can also pass through two or more above-mentioned organic materials of blending, or by admixing for example carbonaceous material and this kind organic material of carbon fiber, for carbonaceous material of the present invention is supplied raw materials.
Carbonaceous material of the present invention can be produced by the above-mentioned Organic Ingredients of carbonization.To carbonization maximum temperature and not restriction especially of soaking condition.For example, in torpescence atmosphere 300-800 ℃ down through preliminary calcining after, carbonization is at least 1 ℃ of firing rate/min, maximum temperature 900-3000 ℃ and carry out under the retention time 0-5 under the maximum temperature hour condition.Preliminary calcining can be omitted.Torpescence atmosphere can be formed by inactive gas, for example comprises nitrogen, argon and helium.Also might use the inactive gas that comprises a small amount of halogen family gas.Be to obtain the shaped form of carbonaceous material, Organic Ingredients can be before preliminary calcining or carbonization, or is forming in preliminary calcining or carbonisation.The carbonaceous material that obtains can also can be used as carbonaceous electrode material by its shaped form after grinding and classifying.Grinding can be before carbonization, after the carbonization or any stage after the preliminary calcining carry out.
More specifically, carbonaceous material of the present invention prepares easily according to following method.
Thereby, grass family (being rice section) Sinobambusa vegetable material under low pressure or in inactive gas atmosphere, carbonization in 1000-1400 ℃ of temperature province.Inactive gas can comprise a small amount of halogen family gas.
On the other hand, the carbon precursor that comes from the grass family Sinobambusa has≤potassium content of 0.5wt%, can be under reduced pressure or in inactive gas atmosphere, carbonization in 1000-1400 ℃ of temperature province.At this, the carbon precursor that comes from the grass family Sinobambusa is among the aftermentioned deliming is handled or can comprise the organic material that comes from the grass family Sinobambusa afterwards, and in calcining or further deliming can comprise the precalcining product that this kind comes from the organic material of grass family Sinobambusa after handling.
The inactive gas that is used for said method can be nitrogen, argon gas, helium or their mixture, can further comprise a small amount of halogen family gas as required, for example chlorine, bromine gas, iodine gas or fluorine gas.Preferred chlorine.The concentration of halogen family gas is preferably about 4-40mol% in halogen-containing inactive gas.
As the preferred carbon source that forms according to carbonaceous material of the present invention, the preferred example of grass family Sinobambusa organic material comprises (parenthetic term is the transliteration of Japanese, and whether has corresponding English (Latin language or Greek) term to have nothing to do regardless of it): Chnequea or Shibataea belong to (Okamezasa), belong to (Shihouchiku), belong to (Narihiradake (Rikuchudake, Narihiradake, Kumanarihira, Medaranarihira, Himeyashadake, Bizennarihira, Kenashinarihira, Yashadake, Nikkohnarihira, Aonarihira)), belong to (Tohchiku (Tohchiku)), Dendrocalamus, Melocanna or Pseudosasa belong to (Yadake (yakushimadake, Yadake, Men ' yadake, Rakkyohyadake)), Sasaella belongs to (Azumazasa (Reikoshino, Johbohzasa, Genkeichiku, Nambushino, Maezawazasa, Suekozasa)), Sasa belongs to (Kumazasa (Kitamikozasa, Miyamasuzu, Geibikumazasa, Rokkohmiyamazasa, Yamatozasa, Yonaizasa, Kuzakaizasa, Kintaizasa, Shakotanchiku, Hushibutozasa, Tanahashizasa, Yasikumasozasa, Gotembazasa, Hatsurohzasa, Ohshidazasa, Himekamizasa, Nambusuzu, Fushigehimekamizasa, Kansaizasa, Miyamakumazasa, Tanzawazasa, Arimakosuzuinusuzu, Kumasuzuhangesuzu, Kesuzu, Kintaichishima, Nemaradidake)), Sasamorpha (Suzudake), Chimobambusa belongs to (kanchiku), bitter bamboo (Pleioblastus) belongs to (Medake (Ryukyuhohiku), Kanzachiku, Taiminchiku, Medakehagawarimedake, Sudareyoshigokidake, Bohshuhnezasa, Azumamezasa, Johhoujidake, Oroshimachiku, Kenezasa), Bambusa belongs to (Sorunii bamboo or Houraichiku (Houraichiku, Shuchiku, Dausanchiku)), and genus (Shichiku).In them, it is preferred belonging to the organic material that bitter bamboo belongs to or Bambusa belongs to.
When stating the Sinobambusa organic material in the use, might use the bamboo of multiple or many genus.
Before carbonization, the organic material that this kind comes from the grass family Sinobambusa preferably in inactive gas atmosphere or under reduced pressure, precalcining in 300-800 ℃ so that remove tar and other volatile matter.This plant material can comprise potassium, its content depends on floristics, the carbonaceous material that raw material by the high potassium content of carbonization obtains has relatively poor performance as carbonaceous electrode material, for example for active matter such as lithium littler anti--contra-doping capacity and bigger non--contra-doping capacity is arranged.
Come from the organic material of grass family Sinobambusa, or from then on plant the carbon precursor that the organic material precalcining obtains and handle the potassium content that can be formed with minimizing by deliming.The potassium content of allowing is maximum 0.5wt%, and is preferred≤0.4wt%, more preferably≤and 0.3wt%, most preferably≤0.2wt%.Carbonaceous material after the carbonization should satisfy this condition, but the precursor that is preferably before the carbonization has satisfied this condition.
Remove potassium (being deliming) preferably by among coarse crushing or afterwards grinding to form particulate from the organic material that comes from the grass family Sinobambusa, and then particulate is immersed for example ash disposal and realizing in hydrochloric acid or the water of acid this kind organic material or tentatively calcine the carbon precursor that this kind organic material forms in about 300-800 ℃ of temperature.If carry out the material that deliming handles bigger particle diameter is arranged, deliming efficient significantly reduces, thereby wants the material of deliming should be preferably the particle form of average grain diameter≤100 μ m, and average grain diameter is μ m more preferably≤50.Deliming is handled and is preferably affacted on the carbon precursor that obtains in about 300-800 ℃ precalcining, so that obtain good deliming efficient.The higher precalcining temperature that surpasses 800 ℃ is not preferred, because it causes deliming efficient to reduce on the contrary.
More specifically, deliming is handled by the material immersion acid of wanting deliming for example in hydrochloric acid or the water, from its extraction and remove potassium and realize.In making the situation of water, preferably at least 50 ℃ of deliming temperature, more preferably 80 ℃ or higher, and lower water temperature causes deliming efficient significantly to reduce.
As for immersion,, repeat to immerse in short-term more effective than carrying out once long-time immersion for improving deliming efficient as the deliming operation.After deliming preferably passes through in immersing acid, immerse 2 times or repeatedly realization in the water.
Carbonization can be carried out as required but be careful, so that do not hinder the formation of loose structure, this structure is that for example hydrogen and methane cause because of tar or analytical product.If carbonization allows to carry out in the dense atmosphere of analytical product, the formation of micropore is insufficient easily, causes carbonaceous material that lower active matter doping capacity is arranged.
Because the existence of vascular, screen casing etc., the organic material that comes from the grass family Sinobambusa were exactly porous originally, in carbonisation, the diffusion of analytical product or move and be convenient to produce a large amount of large diameter relatively holes.
The preferred embodiment of method produced according to the invention carries out carbonization to the carbon precursor that comes from the grass family Sinobambusa, feeds inactive gas or halogen-containing inactive gas (following be referred to as sometimes " processing gas ") simultaneously and contacts with the carbon precursor.In the case, the material (being the carbon precursor) of carbonization to place and carbonization with stacked system in reactor, externally the space feeds inactive gas but contacts (outside-layer feeding scheme) with layer simultaneously; Perhaps, the material (carbon precursor) of carbonization to place and carbonization, feed inactive gas (inside-layer feeding scheme) simultaneously in layer or in the bed with layer or bed.
In outside-layer feeding scheme in batches, the thickness of char-forming material is wanted in the preferred compression of unfertile land as far as possible, so that increase the contact area of material layer and inactive gas, and allows the analytical product of material to remove from system rapidly.Want the cell thickness of char-forming material preferred≤50mm, more preferably≤30mm.Inactive gas with 〉=1mm/sec based on reactor less than speed supply with or feed, preferred 〉=5mm/sec.
Preferred continuous type or the preiodic type inside-layer feeding scheme of using fluid bed, fixed bed etc. that adopt.In this case, inactive gas preferably with every gram want char-forming material 〉=10ml, more preferably 〉=50ml, further the ratio of preferred 〉=100ml is supplied with or is fed, it depends on that time per unit wants the amount of char-forming material simultaneously.Consider the character of product carbonaceous material, preferred higher inactive gas is supplied with ratio, but particularly, the supply ratio is that every gram is wanted char-forming material≤500ml.Indication gas supply ratio is calculated according to the processing gas volume under the standard state (0 ℃ and 1atm) herein.
Carbonization can be carried out under 1000-1400 ℃ of temperature.Cause the product carbonaceous material to increase the capacity of non--contra-doping active matter in the temperature carbonization that is lower than 1000 ℃.The capacity that causes reducing the doping active matter in the temperature carbonization that is higher than 1000 ℃.
Below, anhydrous solvent secondary cell of the present invention is described.
Carbonaceous material according to the present invention has the microstructure that is suitable for elements doped lithium, and can be suitable for use as electrode material of lithium battery to constitute the male or female of the active matter lithium that will mix.Especially preferably constitute negative electrode, with the cathode activity thing of elements doped lithium as the anhydrous solvent lithium secondary battery with carbonaceous material.
Fig. 1 illustrates the anhydrous solvent lithium secondary battery of conduct preferred embodiment of battery according to the present invention with partial enlarged drawing.
More specifically, secondary cell consists essentially of the stepped construction that is impregnated with electrolyte, comprising: anode 1, negative electrode 2 and place anode 1 and negative electrode 2 between and comprise the shim 3 of polymeric material microporous barrier, this polymeric material for example is polyethylene or polypropylene.Stepped construction is twined with the vortex shape and is formed generating element, and this element places the metal-back 5 with the bottom that constitutes cathode terminal 5a.In secondary cell, negative electrode 2 is electrically connected on the cathode terminal 5a, and the battery topmost constitutes with the safety valve 7 that is stamped top board 8 by placing filler 6, and top board 8 has the protuberance that constitutes the positive pole terminal 8a that is electrically connected to anode.Further, the complete sealing unit battery structure of the uppermost margin 5b of shell 5 crimping formation to the inside encapsulation generating element.
At this, anode 1 or negative electrode 2 can be made of the electrode structure 10 with section structure shown in Fig. 2 part.More specifically, electrode structure 10 comprise conductivity substrate 11 and on conductivity substrate 11 at least one surface, be preferably two lip-deep combination electrode layers (12a, 12b) shown in Figure 2, substrate 11 comprises for example metal forming or the woven wire of iron, stainless steel, copper, aluminium, nickel or titanium, and for small size battery, thickness is for example 5-100 μ m or 5-20 μ m, combination electrode layer (12a, 12b) is for small size battery, thickness is for example 10-1000 μ m, preferred 10-200 μ m.
Combination electrode layer 12a and 12b are the layer that is respectively formed on the conductivity substrate 11, wherein comprise according to graininess carbonaceous material of the present invention, comprise the conductive material of conductive carbon for example alternatively and comprise Kynoar for example or the adhesive of vinylidene fluoride copolymers.
More specifically, produce electrode structure 10 (Fig. 2 of above-mentioned anhydrous solvent secondary cell at use carbonaceous material according to the present invention, corresponding with the electrode 1 or 2 among Fig. 1) situation under, carbonaceous material forms the particulate of average grain diameter 5-100 μ m alternatively, then with to the stable adhesive of anhydrous solvent for example Kynoar, polytetrafluoroethylene or polyethylene mix, be coated to conductivity substrate 11 and for example form for example thick layer of 10-200 μ m on the metallic plate of circle or rectangle.Adhesive preferably adds with the ratio of carbonaceous material 1-20wt%.If the amount of adhesive is too much, the electrode of formation has too big resistance easily and battery is formed with bigger internal resistance.On the other hand, if the amount of adhesive is too little, between the particle of material with carbon element and the particle and and conductivity substrate 11 between bonding force not enough easily.Above-mentioned composition and value are that the production according to the relative less secondary cell of size proposes, yet, for the more production of large scale secondary cell, also possible, for example by compression moulding, the mixture of above-mentioned carbonaceous material particulate and adhesive is formed thicker shaped article, and be electrically connected on the shaped article of conductivity substrate.
Carbonaceous material of the present invention is by utilizing its good doping characteristic, the anode material that also can be used as anhydrous solvent type secondary cell, but, be specifically used for constituting above-mentioned will the doping as the negative electrode of the lithium of lithium secondary battery active matter more preferably as the cathode material of anhydrous solvent type secondary cell.
In one situation of back, anode can be by using the metal oxide of selecting according to the target battery model, and metal sulfate or particular polymers constitute as active matter.For example, no lithium metal sulfide or metal oxide TiS for example 2, MoS 2, NbSe 2Or V 2O 5The anode active matter that can be used as the non-aqueous eletrolyte lithium secondary battery, still, in order to constitute the battery of high-energy-density, preferred use mainly comprises Li xMO 2The lithium synthetic, wherein M represents at least a transition metal, x is the numeral of the general 0.05≤x of satisfying≤1.10.The metal M that constitutes the lithium synthesis oxide is preferably for example Co, Ni or Mn.The instantiation of this kind lithium synthesis oxide comprises: LiCoO 2, LiNiO 2, Li xNi yCo 1-yO 2(wherein digital x and y change and generally satisfied 0.7＜x＜1.2 and 0＜y＜1 with charging-discharge condition of related battery) and LiMn 2O 4This kind lithium synthesis oxide can be by grinding and with carbonate, nitrate, oxide or the hydroxide of required mixed lithium and the salt or the compound of another kind of metal, and in 600-1000 ℃ of temperature range in oxidizing gas atmosphere this mixture of calcining and preparing.
The non-aqueous eletrolyte that is used for above-mentioned anode and cathode combination generally forms by electrolyte is dissolved in anhydrous solvent.Anhydrous solvent comprises one or both or multiple organic solvent, for example propylene carbonate, vinyl carbonate, dimethyl carbonate, diethyl carbonate, dimethoxy-ethane, diethoxyethane, gamma-butyrolacton, oxolane, 2-methyl-oxolane, sulfolane and 1, the 3-dioxolanes.The electrolyte that is dissolved in this kind anhydrous solvent to constitute non-aqueous eletrolyte comprises for example salt of lithium, sodium or aluminium of light metal, and this model according to the battery that uses non-aqueous eletrolyte is selected.For example, in the situation that constitutes the non-aqueous eletrolyte lithium secondary battery, electrolytical example can comprise: LiClO 4, LiPF 6, LiBF 4, LiCF 3SO 3, LiAsF 6, LiCl, LiBr, LiB (C 6H 5) 4And LiN (SO 2CF 3) 2Also might use gel form electrolyte, polymer dielectric or inorganic solid electrolyte to replace this kind electrolyte.
As described above with reference to Figure 1, the general following formation of secondary cell of the present invention: promptly staggered relatively the anode 1 of above formation and negative electrode 2, between them, place the shim 3 of the liquid permeable of forming by for example nonwoven fabrics or other porous material alternatively, and anode negative electrode and middle permeable shim are immersed in the aforesaid electrolyte.
More than described as cylindrical battery according to non-aqueous secondary battery embodiment of the present invention.Yet, also other shape can be arranged basically according to non-aqueous secondary battery of the present invention, for example the shape of coin, cuboid or paper or thin slice.
In addition, the measurement of various parameters described herein, promptly with the butanols displacement method measure real density, with helium-displacement method measure real density, with the measurement of nitrogen absorption measurement specific area, hydrogen/carbon atomic ratio (H/C), with x-ray fluorescence analysis measure potassium content, with X-ray diffraction measurement average layer spacing d 002, and carbonaceous material at 0 ℃ CO 2The energy of adsorption force measurement carries out in the following manner.
Measure real density (ρ with the butanols displacement method B)
The real density of carbonaceous material sample by the 1-butanols as replacement media, measure with densimeter according to the method for stipulating among the JISR7212, its main points are as described below.
With about 40ml internal capacity and the specific gravity bottle (densimeter) of the being furnished with side pipe (m that accurately weighs 1).In the bottom of bottle, place sample so that form the flat thickness of about 10mm, measure gross weight (m 2).Slowly add the 1-butanols again and be approximately 20mm until the degree of depth that at the bottom of bottle, measures.Then the slight vibration bottle is put into vacuum desiccator to specific gravity bottle then to confirm big bubble collapse, slowly is evacuated down to 2.0-2.7kPa pressure.This pressure kept 20 minutes at least, after stopping bubble to occur, took out specific gravity bottle.Further inject the 1-butanols, and stopper is put thereon toward this bottle.This bottle further (is controlled at 30 ± 0.03 ℃) in thermostatted water container submergence at least 15 minutes is to be arranged on normal line to 1-butanols liquid level.Take out bottle subsequently and thoroughly clean its outer surface so that accurately to this bottle (m that weighs 4).
In addition individually, identical specific gravity bottle only injects the 1-butanols and is immersed in the thermostatted water container, and the line that sets up standard is subsequently also accurately weighed to obtain quality (m 3).
And specific gravity bottle injects distilled water individually immediately after boiling removes dissolved gases and similarly is immersed in the thermostatted water container, and the line that sets up standard is subsequently also accurately weighed to obtain quality (m 5).
ρ BCalculate by following formula.
ρ B＝(m 2-m 1)(m 3-m 1)d/[(m 2-m 1-(m 4-m 3))(m 5-m 1)]
Wherein d refers to the proportion (=0.9946) of water in the time of 30 ℃.
Measure real density (ρ with helium-displacement method H)
By using " many volumetric ratios restatement 1305 " (Multi-Volume Pycnometer 1305 trade names) that obtain from Micromeritics Co., measure under the maximum 1Pa low pressure, at the ρ of the sample of 200 ℃ of oven dry after 2 hours HAmbient temperature is constant in 23 ℃ in the measuring process.Each pressure that uses in the method is from absolute pressure and deducts ambient pressure and the gauge pressure that obtains.
Measuring instrument (" many volumetric ratios restatement 1305 ") comprises the manometric sample chamber of being furnished with the measuring chamber internal pressure, and the expanding chamber that is connected to sample chamber by the tube connector of band valve.The helium input pipe that has break valve is connected to sample chamber, and the helium discharge pipe that has break valve is connected to expanding chamber.
Measure in the following manner.Sample chamber volume (V CELL) and expanding chamber volume (V EXP) measure with volumetric standard in advance.
Sample is placed in the sample chamber, instrument internal space helium replacement, and helium fed 2 hours from the helium discharge pipe of helium input pipe, tube connector and the expanding chamber of sample chamber.Be closed in valve and the valve in being connected to the helium discharge pipe of expanding chamber (so helium is retained in the expanding chamber with the pressure identical with ambient pressure) between sample chamber and the expanding chamber then.Then, from being connected to the helium input pipe input helium of sample chamber, up to 134kPa, close the break valve in the helium input pipe then until pressure.Measure sample chamber pressure (P when closing behind the break valve 5 minutes 1).Open the valve between sample chamber and the expanding chamber subsequently, helium is transported to expanding chamber so that equal pressure (P to be provided in system 2), and opening measurement in back 5 minutes.
Calculate sample volume (V by following formula SAMP)
V SAMP＝V CELL-V EXP/[(P 1/P 2)-1]
Correspondingly, when sample weight be W SAMPThe time, sample density (ρ H) calculate by following formula.
ρ H＝W SAMP/V SAMP
By the nitrogen absorption measurement specific area
The approximate formula of deriving from BET formula:
Vm＝1/(V-(1-x))，
According to the BET single-point method of using nitrogen absorption, be used under relative pressure x (=0.3), obtaining Vm and (need form the amount (cm of the adsorbed nitrogen of nitrogen monolayer at specimen surface from measured nitrogen volume V 3/ g-sample)).From thus the Vm value that obtains, specific area S BETCalculate based on following formula,
S BET＝4.35·Vm(m 2/g)。
More specifically, the absorption of the nitrogen on the carbonaceous material is carried out under liquid nitrogen temperature in the following manner by using " flow absorption II2300 " (being obtained by Micromeritics Instrument Corp.).
The sample carbonaceous material that grinds to form the about 5-50 μ of average diameter m is filled in coupon, and the cooling samples pipe feeds the helium that contains 30mol% concentration nitrogen simultaneously to-196 ℃, makes the carbonaceous material adsorption of nitrogen thus.Then coupon is returned to room temperature, the amount of the nitrogen of emitting from sample with the heat-conducting type detector measurement obtains the amount V (cm of the nitrogen that is adsorbed thus 3/ g-sample).
Measure potassium content by x-ray fluorescence analysis
Measure for potassium content, prepared beforehand has the carbon sample of regulation potassium content, and measures with making with x-ray fluorescence analyzer and to represent potassium K αThe calibration curve of transmitted intensity and potassium content relation.Use x-ray fluorescence analysis carbonaceous material sample measurement potassium K then αTransmitted intensity obtains potassium content according to calibration curve.Calibration curve is approximately the straight line by initial point in 0-2.5wt% potassium content scope.
The carbon sample that is used to make calibration curve prepares in the following manner.The petroleum coke that does not contain potassium that is prepared into 1200 ℃ of calcinings is ground to form average grain diameter 20 μ m to obtain Powdered carbonaceous material.The saleratus of ormal weight joins in each carbonaceous material and after adding some deionized waters and stirs, the mixture oven dry that obtains.In this way, several carbon samples have been prepared with regulation potassium content.
Use " 3082E2 of RIGAKU system " (obtaining) to carry out x-ray fluorescence analysis in the following manner from Rigaku Denki K.K..Used top irradiation type anchor clamps, the sample measurement zone is arranged in the circle of diameter 20mm.More specifically, the annulus of the high 5mm of diameter 20mm is placed on the filter paper, and 0.935g carbonaceous material sample is placed in the annulus, and surface coverage has parylene's second diester film, and it is measured.By using germanium also to use proportional counter as detector, in 2 θ scopes of 60-73 degree, measure with the 1deg/min sweep speed as analyzing crystal.
The d of carbonaceous material 002
The powdered sample of carbonaceous material is filled in the aluminum sample container, and by the graphite monochromator, uses monochromatic CuK α(wavelength X=0.15418nm) irradiation obtains X-ray diffraction pattern to ray.The peak of diffraction pattern is with gravity model appoach (promptly deciding method corresponding to the peak of position of centre of gravity 2 θ values by obtaining the diffracted ray position of centre of gravity) decision, and (111) the planar diffraction peak value that is used as the high-purity silica flour of standard substance is calibrated.d 002Value is calculated by following Bragg formula.
d 002=λ/(2sin θ) (Bragg formula)
Hydrogen/carbon (H/C) atomic ratio
The carbonaceous material sample carries out elementary analysis with the CHN analyzer, and hydrogen/carbon (H/C) atomic ratio is according to recently calculating based on the hydrogen/amount of carbon atom of hydrogen in the sample and carbon part by weight.
The carbon dioxide adsorption capacity
Use vacuum desiccator carbonaceous material sample 130 ℃ times oven dry in vacuo at least 3 hours, to be formed for measuring the sample of carbon dioxide adsorption capacity, this is measured and uses instrument " Omnisorb 100 CX " (from Coulter Electronics, Inc. obtains).
In order to measure, this kind of 0.2g sample to be placed in the coupon, and to be 10 to the maximum -3In the vacuum of Pa, 200 ℃ of oven dry at least 3 hours, carry out the measurement of carbon dioxide adsorption capacity subsequently.
Under 0 ℃ of adsorption temp setting, according to the constant volume method of measuring the carbon dioxide adsorption capacity, this adsorption capacity is represented with ml/g and (STP) calculating under standard state, the coupon of measuring sample is housed is evacuated down to the maximum 0.4Pa of decompression, import carbon dioxide then, and by sample absorption, till 95kPa equalizing pressure (corresponding to relative pressure 0.027).
Example
Below, according to example and comparative example the present invention is described more specifically.All volumes of following processing gas and flow all be standard state (0 ℃, the 1atm) value of calculating down.
Example 1
The bitter bamboo that is grown in Vietnam is respectively belonged to the bamboo piece, and (size is about 3mm * 3mm * 3mm) and Bambusa and belongs to the bamboo piece (size is about 3mm * 3mm * 3mm) be mixed into raw material with 1: 1 weight ratio, and it is heated to 500 ℃, and in blanket of nitrogen (normal pressure), remain on 500 ℃ and tentatively calcined in following 5 hours, have the carbon precursor of maximum waving of 2wt% thing content with preparation.The carbon precursor is ground to form the powder formed carbon precursor of the about 25 μ m of particle diameter, weight average, and it has the potassium content of 0.5wt%.About 3g powder formed carbon precursor is stacked the thick layer into about 1-2mm in the aluminum crucible, be placed on then in the horizontal tube furnace of diameter 75mm and be heated to 1200 ℃ with 5 ℃/min speed, and keep carrying out in 1 hour carbonization at 1200 ℃, feed nitrogen with 5 liters/min speed simultaneously.
The character of thus obtained carbonaceous material is unified in shown in the following table 1 with the character of the carbonaceous material for preparing in following enforcement and comparative example.
Example 2
The powder formed carbon precursor of preparation in example 1 is carried out the deliming in two cycles handle, wherein each cycle comprises and is immersed in 35% hydrochloric acid 1 hour and cleaned 1 hour in boiling water, to obtain the powder formed carbon of the deliming precursor of potassium content≤0.1wt%.Deliming powder formed carbon precursor is ground once more the powder formed carbon precursor that forms average grain diameter 25 μ m.About 3g powder formed carbon precursor is deposited in the aluminum crucible, is placed on then in the horizontal tube furnace of diameter 75mm and is heated to 1100 ℃, and keep hour carrying out carbonization at 1100 ℃ 1 with 5 ℃/min speed.
Example 3 and 4
With with example 2 in identical mode prepare carbonaceous material, differently be that carburizing temperature is changed into 1200 ℃ (examples 3) and 1300 ℃ (example 4) respectively.
Comparative example 1 and 2
With with example 2 in identical mode prepare carbonaceous material, differently be that carburizing temperature is changed into 800 ℃ (comparative examples 1) and 1500 ℃ (comparative example 2) respectively.
Comparative example 3
The coffee bean that cleaned with hot water keeps carrying out precalcining in 5 hours at 500 ℃ in nitrogen atmosphere (normal pressure), grinds to form the powder formed carbon precursor of average grain diameter 25 μ m then, carries out carbonization in the mode identical with embodiment 1.
Comparative example 4
Palm shell charcoal (obtaining from M.C.Carbon K.K.) is heated to 500 ℃ nitrogen atmosphere (normal pressure), and keeps carrying out precalcining in 5 hours at 500 ℃, obtains having the carbon precursor of maximum 2wt% volatile content.The carbon precursor is ground to form the powder formed carbon precursor of average grain diameter 25 μ m.About 3g powder formed carbon precursor is deposited in the aluminum crucible, is placed on then in the horizontal tube furnace of diameter 75mm and is heated to 1200 ℃, and keep carrying out in 1 hour carbonization, feed nitrogen with 5 liters/min speed simultaneously at 1200 ℃ with 5 ℃/min speed.
Comparative example 5
Phyllostachys (Mohsoh bamboo) (originates in Japanese Fukushima-ken; The age of tree: 3 years, diameter: trunk about 70mm) 600 ℃ of precalcinings 1 hour, ground to form the powder formed carbon precursor of average grain diameter 25 μ m then in nitrogen atmosphere (normal pressure).This powder formed carbon precursor is carried out the deliming in two cycles and handle, wherein each cycle comprises and is immersed in 35% hydrochloric acid 1 hour and cleaned 1 hour in boiling water, to obtain deliming powder formed carbon precursor.Deliming powder formed carbon precursor is ground once more the powder formed carbon precursor that forms average grain diameter 25 μ m.
The powder formed carbon of the deliming precursor of about 3g is stacked into the thick layer of about 1-2mm in the horizontal tube furnace of diameter 75mm, be heated to 1200 ℃, and keep carrying out in 1 hour carbonization, feed nitrogen with 5 liters/min speed simultaneously at 1200 ℃ with 5 ℃/min speed.
The character of the carbonaceous material for preparing in above-mentioned example and comparative example is unified in shown in the following table 1.
The doping of active matter/contra-doping capacity
The carbonaceous material that obtains in example and comparative example is respectively applied for preparation anhydrous solvent secondary cell (element cell), and its performance is estimated with following manner.
Carbonaceous material generally is suitable for constituting the negative electrode of anhydrous solvent secondary cell.Yet, the performance of exact evaluation carbonaceous material for the material property influence of fluctuations that is not subjected to the opposite electrode of phasic property, this performance comprises doping capacity (A), contra-doping capacity (B) and the non--contra-doping capacity (A-B) of element cell active matter, the lithium metal that stability is arranged of excess greatly as negative electrode, every kind of carbonaceous material of above preparation is used as the formation anode, form lithium secondary battery thus, its performance is estimated.
More specifically, anode (carbon electrode) is as following preparation.That is to say that carbonaceous material that 90 weight portions are prepared thus with particulate form and 10 weight portion Kynoar and N-N-methyl-2-2-pyrrolidone N-are mixed together and form the pasty state compound, subsequently this compound evenly are coated on the aluminium foil.15mm diameter circle dish type carbon containing film is peeled off and be embossed into to this compound from aluminium foil after oven dry.Independently, with 17mm diameter circle dish type stainless (steel) wire spot weld 2016 sizes (being diameter 20mm * thickness 1.6mm) coin shape element cell shell in cover, the disc of above-mentioned preparation contained carbon film is pressurized to be bonded on the disc stainless (steel) wire, comprise the anode of about 20mg carbonaceous material with formation.
On the other hand, negative electrode (lithium electrode) preparation with the following methods in the glove box of argon atmospher.17mm diameter circle dish type stainless (steel) wire is spoted weld outer the covering of 2016 size coin shape element cell shells, the impression thick metal lithium sheet of 0.5mm and pressurized being bonded on the disc stainless (steel) wire of 15mm diameter lithium disk that form forms negative electrode.
Thus Zhi Bei anode and negative electrode, place between them porous polypropylene film as shim, comprise propylene carbonate and dimethoxy-ethane 1: 1 (volume ratio) admixture solvent electrolyte and rise ratio solvent in LiClO wherein with 1mol/ 4, in the argon glove box, form the coin shape anhydrous solvent lithium secondary battery of 2016 sizes with the filler of making by polyethylene.
In the lithium secondary battery that constitutes thus, the carbonaceous material in the anode carries out the doping and the contra-doping of lithium, to estimate its capacity.
More specifically, mix by repeating to comprise that 1 hour current density is 0.5mA/cm 2Conduction and the circulation that paused in 2 hours, the equilibrium potential up between the anode negative electrode reaches 4mV and realizes.Thereby the electric current that feeds obtains doping capacity (A) divided by the weight of carbonaceous material, represents with Ah/kg.Then in a similar manner, feed electric current in the opposite direction, from the carbonaceous material contra-doping lithium that has mixed.Contra-doping is by repeating to comprise that 1 hour current density is 0.5mA/cm 2Conduction and the circulation that paused in 2 hours, dropping to cut-ff voltage is that 1.5V realizes.Thereby the electric current that feeds obtains contra-doping capacity (B) divided by the weight of carbonaceous material, represents with Ah/kg.Calculate non--contra-doping capacity (A-B) then when having difference between doping capacity (A) and the contra-doping capacity (B), also multiply by merchant (B/A) with 100 obtains discharging efficiency (%) to remove contra-doping capacity (B) with doping capacity (A).Discharging efficiency is effectively to utilize measuring of active matter.
Performance with the lithium secondary battery of the various carbonaceous material anodes of measuring is in the above described manner summed up in following table 2.
With reference to result shown in the table 2, can think, the secondary cell that the carbonaceous material that obtains from example of the present invention by use prepares has highly doped capacity, high contra-doping capacity, and very little non--contra-doping capacity is arranged when having difference between doping capacity and contra-doping capacity, thereby can effectively utilize the element cell active matter.
The secondary cell that obtains with the carbonaceous material of comparative example 1 bigger doping capacity is not only arranged and also have very large non--the contra-doping capacity, thereby have the active matter lithium and can not get the difficulty effectively utilized.
The secondary cell that obtains with the carbonaceous material of comparative example 2-5 has littler contra-doping capacity.
Table 1: the character of carbonaceous material
Parent material Carburizing temperature (℃) ρ B (g/cm 3) ρ H (g/cm 3) H/C SBET (m 2/g) K content (%) d 002 (nm) *1 A CO2 (ml/g)
Example 1 Bamboo mixes *2 1200 1.43 2.10 0.07 2.0 0.52 0.385 25
Example 2 ″ 1100 1.45 2.10 0.10 2.7 0.12 0.394 65
Example 3 ″ 1200 1.42 2.14 0.07 1.3 0.12 0.388 53
Example 4 ″ 1300 1.42 2.11 0.06 1.0 0.11 0.387 25
Comparative example 1 Bamboo mixes *2 800 1.45 1.71 0.23 63 0.14 0.396 68
Comparative example 2 ″ 1500 1.41 1.52 0.02 0.8 0.09 0.373 1
Comparative example 3 Coffee bean 1200 1.45 1.52 0.03 3.2 0.80 0.377 2
Comparative example 4 Cocoanut shell 1200 1.48 2.07 0.03 1.1 0.92 0.389 15
Comparative example 5 Phyllostachys 1200 1.47 2.11 0.05 3.0 0.10 0.388 6
*1 A CO2: carbon dioxide adsorption capacity (ml (STP)/g-carbon)
*2 bamboos mix: bitter bamboo genus and Bambusa belong to the mixture of 1: 1 (weight ratio)
Table 2: battery performance
Doping capacity (A) (Ah/kg) Contra-doping capacity (B) (Ah/kg) Non--contra-doping capacity (A-B) is (Ah/kg) Discharging efficiency (%) (B/A) * 100
Example 1 595 490 105 82.4
Example 2 775 630 145 81.3
Example 3 710 580 130 81.7
Example 4 560 500 60 89.3
Comparative example 1 805 450 355 55.9
Comparative example 2 370 325 45 87.8
Comparative example 3 507 407 100 80.3
Comparative example 4 538 437 101 81.2
Comparative example 5 550 460 90 83.6
Commercial Application
As mentioned above, can obtain having the carbonaceous material of large doping capacity and large contra-doping capacity according to the present invention. The organic material that comes from the grass family Sinobambusa by carbonization under suitable Carbonization Conditions is produced this kind carbonaceous material easily. Negative electrode by using carbonaceous material according to the present invention to prepare might provide the non-aqueous secondary battery with the excellent properties that comprises large charge/discharge capacity.

Claims (9)

1. a carbonaceous electrode material that is used for non-aqueous secondary battery wherein comprises a kind of carbonaceous material, and this carbonaceous material has: be measured as≤1.46g/cm with the butanols displacement method 3Real density; Be measured as 〉=1.7g/cm with helium-displacement method 3Real density; Be measured as≤hydrogen-carbon atomic ratio H/C of 0.15 with elementary analysis; Be measured as≤50m with nitrogen absorption BET method 2The BET specific area of/g; And 〉=the carbon dioxide adsorption capacity of 10ml/g, and this carbonaceous material obtains by the organic material that carbonization comes from the grass family Sinobambusa, this organic material that comes from the grass family Sinobambusa comprises and at least aly comes from that bitter bamboo belongs to and the organic material of Bambusa genus.
2. carbonaceous electrode material as claimed in claim 1, the wherein potassium content≤0.5wt% that measures with x-ray fluorescence analysis.
3. method of making carbonaceous electrode material as claimed in claim 1, comprising: the described organic material that comes from the grass family Sinobambusa of carbonization under low pressure or in inactive gas atmosphere, under 1000-1400 ℃ of temperature, described inactive gas is nitrogen, argon gas, helium or their mixture.
4. method as claimed in claim 3 wherein further comprises: be used for the wet processed organic material so that the deliming treatment step of the potassium content≤0.5wt% that measures with x-ray fluorescence analysis to be provided.
5. method as claimed in claim 3, wherein said inactive gas also comprises halogen gas.
6. electrode structure that is used for anhydrous solvent type secondary cell is comprising: conductivity substrate with place at least one lip-deep combination electrode layer of conductivity substrate; And
This combination electrode layer comprises the carbonaceous electrode material and the adhesive of particle form,
This carbonaceous electrode material comprises a kind of carbonaceous material, and this carbonaceous material has: be measured as≤1.46g/cm with the butanols displacement method 3Real density; Be measured as 〉=1.7g/cm with helium-displacement method 3Real density; Be measured as≤hydrogen-carbon atomic ratio H/C of 0.15 with elementary analysis; Be measured as≤50m with nitrogen absorption BET method 2The BET specific area of/g; And 〉=the carbon dioxide adsorption capacity of 10ml/g, and this carbonaceous material obtains by the organic material that carbonization comes from the grass family Sinobambusa, this organic material that comes from the grass family Sinobambusa comprises and at least aly comes from that bitter bamboo belongs to and the organic material of Bambusa genus.
7. electrode structure as claimed in claim 6, the potassium content≤0.5wt% with the x-ray fluorescence analysis measurement of wherein said carbonaceous material.
8. anhydrous solvent type secondary cell, comprising: anode, negative electrode, shim and place anode and negative electrode between non-aqueous eletrolyte; And
In described anode and the negative electrode at least one comprises following electrode structure, and this electrode structure comprises: conductivity substrate and place at least one lip-deep combination electrode layer of conductivity substrate;
This combination electrode layer comprises the carbonaceous electrode material and the adhesive of particle form,
This carbonaceous electrode material comprises a kind of carbonaceous material, and this carbonaceous material has: be measured as≤1.46g/cm with the butanols displacement method 3Real density; Be measured as 〉=1.7g/cm with the nitrogen displacement method 3Real density; Be measured as≤hydrogen-carbon atomic ratio H/C of 0.15 with elementary analysis; Be measured as≤50m with nitrogen absorption BET method 2The BET specific area of/g; And 〉=the carbon dioxide adsorption capacity of 10ml/g, and this carbonaceous material obtains by the organic material that carbonization comes from the grass family Sinobambusa, this organic material that comes from the grass family Sinobambusa comprises and at least aly comes from that bitter bamboo belongs to and the organic material of Bambusa genus.
9. anhydrous solvent type secondary cell as claimed in claim 8, the potassium content≤0.5wt% with the x-ray fluorescence analysis measurement of wherein said carbonaceous material.
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